Metal compounds of azo dyestuffs



Patented Nov. 12, 1940 UNITED STATES 2,221,361 METAL COMPOUNDS OF A ZODYE-STUFFS Max Schmid, Riehen, near Basel, Switzerland, as-

signor to the firm Society of Chemical Industry in Basic, Basel,Switzerland No Drawing. Original application September 27,

1937, Serial No. 166,021. Divided and this application March- 23, 1939,Serial No.

Switzerland October 3, 1936 17 Claims.

This application is a division of my application for Patent Serial No.166,021, filed in U. S. A. on September 2'7, 1937 and. in Switzerland onOctober 3, 1936.

According to this invention valuable products are obtained by treatingwith an agent yielding metaL-such as a compound of copper, chromium,nickel, iron or cobalt, in substance or on the 10 fibre, an azo-dyestuffwhich is obtainable by the action of such a diazo-compound of thebenzene and naphthalene series which contains inortho-position to thediazo-group a substituent which is capable of forming stable lakes withthe azo-group formed, such as an orthohydroxy or ortho-carboxy-diazocompound on a 1-aryl-5-pyrazo1one which itself is obtainable bycondensation of a fl-carbonyl-carboxylic acid ester with a hydrazine ofthe general formula in which 11 represents a -CH=CH-group or a-CHzCH2-group and z rep-resents a group which is formed by reduction ofa nitro-group in combination with a condensation, such as an azoorazoxy-group or an amino-group substituted by the residue of an organicacid. The new azo-dyestufis containing metal thus obtained aredistinguished by the high iastness to light of their dyeings and bytheir excellent afiinity for vegetable fibres, such as cotton, flax,ramie, and for fibres of regenerated cellulose,

zene, 1-hydroxy-2-amino-5-nitrobenzene,l-hydroxy-2-amino-4;G-dinitrobehzene, l-hydroxy-Z-amino-5-nitro-6-chlorbenzene, l-hydroxy-Z-amino-4-methyl-benzene,1-hydroxy-2-amino-4-nitro-S-chlorbenzene,l-hydroXy-Z-amino-l-nitrobenzene-G-sulfonic' acid,l-hydroxy-z-amino-finitrobenzenel-sulfonic acid,l-hydroxy-Z-aminobenzene-i-sulfamide, 1'- hydroxy 2aminonaphthalene-4:S-disulfonic acid, 2-hydroxy-1-aminonaphthalene-4-sulfonic acid, 2-hydroXy-1- anfino-B-nitronaphthalene4 sulfonic, acid, 1- aminobenzene 2 carboxylic acid,l-amino-lchlorbenzene-Z-carboxylic acid,l-amino-e-nitrobenzene-2-carboxy1ic acid,l-aminol-benzoylamino-Z-carboxylic. acid,4-amino-3-carboxylica-zobenzene-i-sulfonic acid, .aminosulfobenzoic acid(NHzZl, COOI-Iz2, SO3H:4), Z-aminonaphthalene-B-carboxylic acid, and soon.

Among the pecarbonyl-carboxylic acid esters availablefor preparing the1-aryl-5-pyrazolones which canbe usedior the synthesis of the parentdyestufis there may be named formy'l acetic acid esters, furthermorepketorcarboxylic acid esters, such as ethyl-aceto-acetate, ethyloxalacetate, ethylbenzoylacetate, terephthaloyldiacetic acid ethyl ester,and so on.,- Among thelhydrazines which likewise, are used for preparingthe l-aryl-S-pyraz'olones used for the synthesis of the parent dyestuffsthere may be named such products as:

such as artificial silks, for example viscose arti- 03H ficial silk orcuprammonium artificial silk.

Among the ortho-hydroxy and ortho-carboxydiazo compounds which come intoconsideration S031; 40 for the preparation of the azo-dyestuffs formingl the parent materials of the invention there may NHrNH CH=CH be namedquite generally those derived from ortho-aminophenols orortho-aminonaphthols or ,s l S from ortho-aminocarboxylic acids of thebenl 45 zene or naphthalene series, for example l-hy- NHFNH 011F011droxy 2 aminobenzene, 1-hydroxy-2-amino-4- chlorbenzene, 1 hydroxy 2amino-4-nitroben- 0,11 l s 03H Quite generally, however, it is moreadvantageous first to combine the nitrohydrazine or the aminoi hydrazinewith one vof the aforesaid c-carbonylcarboxylic acid esters and then toconduct the I. I N No, reduction of the nitro-group in combination with,V c

a condensation reaction. -'Ih'is may occurr, for 0 example, by cautiousreductionby meansoigrape Q sugar, the course of the reaction beingpresumed to consist in the reduction of a part of the product r i to theamino-group, which then condenses-with CH the unreduced or onlypartially reduced portions i to produce an azo or azoxy compound; the p1 K protection of such dyestuffs is the object of "my l NQCHr-CH NO;

application Serial No. 263,796, of March 23, 1939, O which, like thepresent application, is also a divill sional application ofmyapplication Serial No. 166,021,;filedSeptember 27, 1937-, ortheoperation may consist in complete reduction of'thev nitrogroup totheNHz-group "and subsequent conden (4) O sation, for example witheahalogen' compound I which converts the NI-IrEIOIlp-intO a. i \N1;:11-0-5 p a T a l l i 08H ,03H';

H S 03H CH=CH No;

group in which a stands for metalloid whose atomic weight is notlessthan 14 and not greaterthan l6, and 1) stands for an organic residue ofthe aliphatic, aromatic, cycloaliphatic, heterocyclic, araliphaticseries and'so on. Such pro-ducts coni stitute acyl derivatives or, theamidines which (5) chemically are closely 'related' thereto. As is CH3known, the introduction of suchresidues into in- (|:=N I i termediateproducts or dyestuffs increase, the

afiinity for vegetable fibre. 7 Such residues can be OH=CH introduced byacylation, for example by treatment B, -c with benzoylchloride;phenylacetyl chloride, cin- O 03H namyl chloride, succinyl chloride,butyryl chloride, hexahydro-benzoyl, chloride, furane-carboxylic acidchloride, benzimino etheiyby treatment with (6 i "40 subject of myparent application Serial No. 166,021 CH1=CH R filed Sept. 27, 1937 orthiophosgene or by treat- .V I

, phosgene (the'dyestufis which may be prepared coon 1 by treatment withphosgene' are particularly the ment with heterocyclic products of thenature of H1 amidine halides, such as cyanuric acid chloride, or

cyanuric acid bromide, tribromopyrimidine, 2 6- dichloro-4methylpyridine, 'dichloroquinazoline, I V

and so on. The present application now has for (7) a H z v 7 itsparticular aim the protection of such dyestufis 2 acontaining'heterocyclic rings." r l 1 Particularly valuable productsresult when the condensation is conductedin such a manner that theresidue h is so constituted that it contains an i i azochromophore or isadapted to couple with I N oH=o H, 55 diazo compounds to produceazo-dyestuffs. 'I'here a are thus obtained 1-aryl-5-pyrazolones in whichg SOaH 03H the aryl residue has the general formula:

(s) on; p OaH SOaH IEII in which y stands for a --CH =CH- or a l Q Q fiCH2-CH2-group andzstands foranitro-group H2 -0 o in combination with acondensation. Such g pyrazolone derivatives are, for example:

CHI I i 4 C a v v l \N CH=CHQNQ.2 I \N CH=OH i r- 0 Hz -o f 1 mo-o H A:11 803E 02H SOIH H: C h N ll s0|H osn s 0 5* EN- (20) CH: 7 l NQCH=CH Wemu From a comparison of the pyrazolone nuclei of the products of theFormulae 1-7 with those of the products resulting from the reduction ofa f nitro-group together with a condensation shown in Formulae 5-20, allof which are given by' way of example, it is evident how numerous arethe intermediate products for making the dyestufi's forming the parentmaterials for the invention; regard must further be had to the fact thatthe aryl residue of the pyrazolones may belongeither to the stilbene orto the dibenzyl series. It is also possible first to convert thel-aryl-5-pyrazolones from the aforesaid nitroor amino-hydrazines bycoupling with one of the diazo compounds al-* ready referred to intoazo-dyestufi's of the general formula:

in which R stands for an aromatic nucleus of the benzene or naphthaleneseries, .2: stands for an OH- or a COOH-group which stands inorthoposition to the --N=N-group, 2; stands, for instance, for hydrogen,alkyl, aryl, COOH or COOR' (R'=a1kyl), y for a CH=CH- or aCHz-CHz-group, and z for a N02- or NI-Iigroup, and then to proceed withthe conversion of the nitroor amino-group.

The combination of the aforesaid coupling components and diazotizedortho-hydroxylated "orortho-carboxylated diazotization components to;produce azo-dyestufis proceeds, as is usual for" pyrazolones, in an acidor an alkaline medium. As will be apparent from the foregoing formulaeof the coupling components, besides the formacou'pling components are,also different.

qlute generally the diazotized ortho-aminocarcombining ,1

. .azotized miss GOOH

tion of the "pyrazolone-azo-dyestufi a further azo-dyestufi formationmay occur, for example with the residue of one of theaminophenol oramino-hydroxy'naphthalene derivatives named (see for instance Formulael3 and 20) In this case it is possible to prepare as may be desiredmixed dyestuffs in'respect of the diazotization components, since, apartfrom the different coupling powers of the diazo'components, the

coupling powers of the Various residues of the Thus,

boxylic acids couple more easily than the diazotized ortho-amino-hydroxycompounds and the pyrazolones more easily than thel-hydroxynaphthalene-3-sulfonic acid residues. Thus, by

mol of diazotized l-aminobenzene-z-carboxylic acid in an acetic acidmedium-with 1 mol of'the compound of the Formula -.l9, and thenvcombining the mono-azo-dyestuff further in an alkaline medium with 1mol of di- 1-hydroxy-2-aminobenzenel-sulfonic acid, there is produced adyestuff of the, formula:

LN m Such mixed dyestuffs, but. containing metal, may also be preparedeasily by the use of diazotization components which only duringmetallisation pass into ortho-hydroxyor orthocarboxy-azo derivatives.

"I'he conversion of the azo-dyestufis into metal compounds may as a rulebe conducted by treatment of the finished dyestufi with a salt, hydroxide or o ;ide of one of the metals hereinbefore referred' to forexample copper sulfate, copper chloride; copper hydroxide, ammoniacalcopper oxide, -copper tetramine sulfate, deriva- "tives of coppertetramine sulfate in which the z mmonia residues are replaced by theresidues of organic bases, such as methylamine or pyridine, chromiumchloride, chromium sulfate;

chromium fluoride, chromium formate, chromium acetate, chromiumhydroxide, sodium chromite, sodium glycerine chromite, nickel chloride,nickel sulfate, cobalt chloride, manganese chloride, and so on. Themetallisation may be conducted on-thefibre or advantageously insubstance by treating or warming a solution or suspension of thedyestuif in admixture with one of the aforesaid salts in an open vesselor under pressure. The same metalliferous dyestuffs can also be obtainedby metallising dyestuffs which have. been prepared from the1-aryl-5-pyrazolones here in question and from diazotization componentswhich contain no OH- or COOH- group in ortho-position but contain inorthoposition a substituent which in the course of the metallisation,becomes converted into an 01-1- or C0O'H group, such as a chlorine orbromine atom or an OCI-Iz-group (which substituents are converted intothe OH-group during metallisation) or a COO-alkyl-group which is thensaponified to a COO'H-group. The metallization can also occursimultaneously with the coupling of the azo-dyestuff; this procedure isparticularly to be recommended in the production f coppercompounds. l

Thenew dyestufis, therefore, which are ob jectsqof, the presentdivisional application are complexmetal compounds of dyestuffs such asthegfollowing:

ponents hereinbefore mentioned and the formulae of the couplingcomponents given by way of example.

The dyestuffs of the present invention are accordingly complex metalcompounds of 8230-, dyestuffs of the general formula in which :1: standsfor a substituent in ortho- I I v 80111 f'Qa and, in i-position with theazo-residue: y for a CH=CH- or a CHz-CHz-group and z for the con--version product of a nitro-group.

The characteristic properties of the new metalliferous dyestuffs areconditioned by the grouping SOaH $0311 which in particular isresponsible forthe shade of the dyestuffs, their high fastness to lightand their affinity for vegetable fibres, as will be evident from acomparison of the properties of the individual products described in theexamples which follow.

When prepared in substance the new products in an'acetic acid mediumwith 45.1 parts of the 3-methyl-5-pyrazolone of the formula The dyestufiis isolated, dissolved in 1000 parts of water, containing an excess ofsodium carbonate, and the solution is treated with phosgene at 40-50" C.When this treatment is ended, that is to say when a free amino-group isno longer present, the dyestuff is isolated and dried.

It is a. yellow powder which dyes cotton 'i'ast yellow shades.

The dyestuff thus prepared is suspended in 3000 parts of water and thesuspension is mixed with an ammoniacal copper oxide solutioncorresponding with parts of crystallized copper sulfate. The whole isstirred at 60-70 C. for about 1 hour, whereupon the metalliferousdyestuif is filtered with suction and cautiously dried. The dry dyestuifcontaining copper is a brown powder which dyes vegetable fibres andartificial silks of regenerated cellulose excellent yellow shades fastto light. The non-metallised dyestulf corresponds thus to the formula SOaH S OaH (1: S 0 11 S 03H =N I l N@CH. CH. NH. I Hz C v I I ll treatingthe. dyestuff with phosgene and converting the product into thecomplex'copper compound as above described there is obtained a dyestuifcontaining copper which, when dried,

constitutes a yellow-brown powder and dyes cotton fastyellow shades,resembling in shade and properties those of the stilbene product.

By suspending 59.9 parts of the dyestuif described in the' firstparagraph of this example in about 3000 parts of water and treating thesuspension with a solution of 30 parts of crystallized nickel sulfate in200 parts of water for 1 hour at 70--80" C. in the presence of sodiumacetate there is obtained the complex nickel compound of the dyestuifwhich, when dried, is a brownish powder which dyes cotton fast yellowshades with a somewhat orange hue.

The same shades are obtained by first dyeing with the nonmetallizeddyestuif in the manner usual for dyeing with direct dyestuifs and thenafter-coppering or after-treating the dyeing with a nickel salt. Bytreating with aniron salt a dyeing prepared with an alkali salt of thedyestuff there is obtained a dull yellow shade, by treatment with acobalt salt a yellow shade, with a chromium salt a somewhatgreenish-yellow shade and with a manganese salt a yellow shade.

ExampZe'Z i 45 parts of the 3-methyl-5-pyrazolone of the formula,dyestufi described in the preceding or of the formula x freeamino-group has disappeared the urea is isolated. 1

46.2 parts of the urea thus obtained are dis-' solved in water togetherwith the quantity of sodium carbonate necessary for forming the sodiumsalt, 13.6 parts of sodium acetate are added and the solution is coupledin the usual manner with a solution of the diazo compound from 13.7parts of 1 aminobenzene-2-carboxylic acid in the presence of 25 parts ofcopper acetate. When the diazo compound has disappeared the whole ismade alkaline with ammonia, gently heated and filtered after theaddition oi common; salt. The cupriferous dyestulf thus obtained showsthe same behaviour as the cupriferous' example. The replacement ofphosgene by thiophosgene leads to a similar product. Similar dyes areobtained upon the replacement o'f the l-aminobenzene-Z-carboxylic acidby the 1-amino-4 ch1'orobenzene-Z-carboxylic acid, byl-amino-l-nitrobenzene-Z-carboxylic acid, by l-arninol-methylbenzene-2-carboxylic acid or by1-amino-4-ethoxy-benzene-Z-carboxylic acid. If there is used as parentmaterial for making the metalliferous dyestulf the3-carbox'y-5-pyrazolone of the formula "I'ooog' 1 I j.

SOaH' SOaHj I v V /N CH=OH H: -(R J.

obtainable by condensation of the corresponding hydrazine withoxalacetic ester or its. sodium compound and saponification of thecarboxylic ester group, or the 3-phenyl-5-pyrazolone of the formula(obtainable from b enzoylacetic ester), dyestuffs having similarvaluable properties are obtained.

Theformula of a non-metallizedl dyestuff of this. groupisforinstance v IEmample3 59.9 parts. of thedyestuff from diazotized 1- 5 0003 coon N=Cc0011 N=NCC 1k H, o --N=N l SOaH SOSH sour SOaH g 10 p H Quite similardyestuffs are obtainedlif the CO- aminobenzene-Z-carboxylic acid and the3-methgroup of the urea residue is replaced by a..heteroyl--pyrazo-loneof the formula cyclic amidine-like nucleus. Such a product can beobtained, for example, by adding 902 parts I of the3-methyl-5-pyrazolone named in the first paragraph of this example to afineaqueoussus- N GH=CH NH: pension of 18.4 parts of cyanuric chloridecare HE being taken to keep the reaction mass just neull S0911 0311 tralby the addition of a sodium carbonate so- 0 lution. When no more sodiumcarbonate is conin the form of the neutral sodium salt are dissumed thesecondary condensation product from solved in about 300 parts of water,and at 0-5 C. 2 mols of the pyrazolone and 1 mol of oyanuric thesolution is introduced into an aqueous suschloride has been formed. Ifrequired, this secpension of 18.4 parts of cyanuric chloride. When 25ondary product can be convertedinto a tertiary condensation is finishedthere is introduced into condensation product by "replacing the romainthe mixture a solution of the sodium compound ing chlorine atom in thecyanuric fringbytre'atfrom 25;? parts of 4-amino-4-hydroXy-azobenmentwith 9.3 parts of aniline in known manner. zene -3-carboxylic acid inabout 100 parts of wa- If now the sodium salt from 53.5 partsof this tenThe whole is heated at 50-55 C. and the 30 condensation product iscornbined 'with the diazo liberated acidis neutralized by the additionof compound from 13.7 partsof l a'rn-inobenzene-zsodium bicarbonate.When condensation is fine carboxylic acid there is obtained a dyestuffwhose ished the reaction product is salted out and iiimetal compoundsresemble the metal compounds tered with suction. The dyestufi of theformula r coon l l H 40 0: \(l3/ of the azo-dyestufi of EXa ir plev 1'for tame; can be converted as such into a metal compound; 45 the coppercompound dyes cotton lowf 'sliades" the copper compound dyes. cotton orviscose artivery fast to light. The formula of'the nonni'etiicial silk,for example, fast yellow shades.

allized dyestuff is therefore: The third chlorine atom of the cyanuricring CH: i 311; 50

L \N -CH= CH=CH-QN i N=N o o- N=N II 80:11 0311 l I O HH COOH H000 55 If3 p g fli y m f may also be exchanged. For this purpose the 5:1? ini?cilforff r i flfg3 1 freshly filtered non-metallized dyestufi is dis- 60an Cy c 1 l j solved in about 800 parts of water and the solutionderived the 18.4- parts of cyanuric chloride are l is boiled for about 1hour with 9.3 parts of aniline replaced by 11.5 partsof2.6-dichloro-4-methyl- ,l l for replacing the remaining chlorine atom ofthe pyrimidine or 19.9 partsotdmhloro-qumazolme y or 21 4 parts ofphenylchlorotriazinei dyestufis cyanuric residue. The excess of anilineis then 65 having very similar properties-are obtained.- The: ggz gigz gg g fi g ggi fiis g zg fi fi g iormula of suchv a non-metallizeddyestuff. is: y V

on; Y 011;

I fiQ r l f ll ii $011 I ton H sous son :N H o a H o J 1 3 on dyescotton powerfullyellow. shades.

This dyestuiT having presumably the formula is suspended in about 3000parts of water and the suspension is mixed with an ammoniacal copperoxide solution corresponding with 50 parts of crystallized coppersulfate. The whole is heated at 60'70 G. and stirred for about 1 hour atthis temperature. The sparingly soluble complex copper compoundprecipitates and after cooling group is merely replaced by aCHz-CHz-group If the dyestufiz' of the v has similar properties. firstparagraph of this example is suspended in about 3000 parts of water andthe suspension is 1 heated with a solution of 30 parts of crystallizednickel sulfate in 200 parts of water in the pres-@- ence of sodiumacetate for one hour at IO-80 0., there is obtained a complex nickelcompound which, when dry, is a brownish powder and dyes cotton-fastyellow tints. 4 j 1 Like shades are obtained by first dyeing the fibrewith the non-metallized dyestufi linthe manner usual for directdyestufis and then aften-- coppering the dyeing or after-treatirigitwith a nickel salt in known manner. ,By treating with an iron salt adyeing produced by meansio'f analkali salt of the dyestuif there areobtained dull suction and dried. The dyestufi so obtained yellow,shades; by treatment with cobalt saltsl yellow shades, with chromiumsalts somewhat greenish-yellow shades and with manganese salts yellowshades are obtained. Those complex meta1 salts "may also be, prepared insubstance by.

known methods.

By-metallizing according to the data of the preceding paragraphs thesimilarly constituted dyestuftof the formula which is obtained as chiefproduct if phosgene is run into a solution of 60 parts of theazo-dyestuii' of'the iormula OOH and 26 parts of4-amino-4'-hydroxyazobenzene- 3'-carboxy1ic acid in 400 parts of watercontaining 30 parts of sodium carbonate until almost no free amino-groupis present, there are obtained dyestufl's whose tints are very similarto the corresponding metallized dyestufis containing the cyanuric ring.n

The. replacement of l-aminobenzene-2-carboxylic'acid by anortho-aminophenol or an ortho-aminonaphthol in the-synthesis of suchdyestufis leads to copper compounds which dye brown shades. .This :isthe case, for example, with the dyestufis of the general formulae andCOOCIHB S0115: BOtH C=N\ l SOaH- N=NC-C l [I 00011 H OH in which :0stands for instance, for shades and can be converted into a complex cop-NCN per compound in the manner already described. l The replacement ofthe 4-amino-azobenzene-4- and sulfonic acid by the azo-dyestuff fromdiazotized 2 amino-naphthalene-4:8-disulfonic acid and f fi fmeta-toluidine followed by diazotization and 0011- H N N H pling with afurther molecule of meta-toluidine leads to a product which whenconverted into the Finally, if in the first phase of this example IS0311 S 03H the primary condensation product of the formula (I) I l Q QWN 43-0 A H N N H copper compound constitutes a browner dyestufi, whichcorresponds for example to the following formula of a non-metallizeddyestuff:

' scan Example 4 The primary condensation product prepared according tothe first paragraph of Example 3 from 1 equivalent proportion of thedyestufi from diazotized l-aminobenzene-Z-carboxylic acid and the1-aryl-5-pyrazolone of the formula and one equivalentproportion ofcyanuric ch10 ride is condensed in an analogous manner with of4-amino-azobenzene-4' -sulfonic 27.? parts acid and 9.3 parts of anilineor 10.7 parts of mono-methylaniline or para-toluidine. There is obtaineda yellow dyestuff which dyes cotton fast Example 5 45.1 parts of the3-methyl-5-pyrazolone of the formula or of the formula CH3 5 S03]?!S0311 =N v I I /N CH2-CH NH2 H2 0 l H a in the form of the neutralsodium salt are condensed in known manner with 48.4 parts of cyanuricchloride and the primary condensation product is combined with asolution containing 23.9 parts of2-amino-5-hydroxynaphthalene-'lsulfonic acid in the form of the sodiumsalt at 40-50 C. whilst neutralizing the acid liberated in thecondensation by means of sodium carbonate. For exchanging the remainingchlorine atom of the cyanuric ring the secondary condensation product istreated in known manner with 9.3

lene-7-sulfonic acid are replaced by a like quantity of2-amino-S-hydroXynaphthaIene-G-sulfonic acid there is obtained adyestuff containing copper and dyeing similar shades, whilst replacementof the Z-amino-5-hydroxynaphthalene-7- sulfonic acid by 31.9 parts ofl-amino-8-hydroxynaphthalene-3:fi-disulfonic acid leads to a prod- 13.7parts of 1-amino-benzene-2-carboxylic acid or of the formula uctcontaining copper which dyes appreciably (IJHB SOH SCH 20 i a a deeperand redder shades. The formula of the non-metallized dyestuffcorresponding to the last named product is the following:

are dissolved in 200 parts of water with addition of sodium carbonate inthe quantity required for forming the neutral sodium salt and the solu-OHa I SOaH C=N\ I l w 35 N=N -o H N N H I SQaH SOaH HOW H I v C 00011 1G I N Y ll 40 COOH tion is then mixed with the diazo solution from Deepbrown is for example the copper compound of. the azo-dyestufi of theformula Complex metal compounds which dye yellow shades can be obtainedby replacing in the preparation of the intermediate product the 2-amino--hydroxynaphthalene-7-su1fonic acid by l-amino-3-hydroxynaphthalene, 1-(4-aminophenyl) 3-methyl-5-pyrazolone, 1-(3'-aminophenyl)- 3carboxy-5-pyrazolone, para-amino-aceto-acetic anilide and so on. Theformula of such a nonmetallized dyestuff is for example:

with the addition of a solution of 25 parts of copper sulfate in diluteammonia. There is thus formed the copper compound of the disazo-dyestuffwhich, when isolated in known manner, dyes cotton fast brown shades. Ifin the preparation of the intermediate product for this dyestufiaccording to the first paragraph of this example the 23.9 parts of2-amino-5-hydroxynaphtha- OOH 7 Example 6 42.9 parts of the ternarycondensation product of the first paragraph of Example 5 are dissolvedto a neutral solution which is mixed with a diazo solution from 6.9parts of l-aminobenzene-Z- carboxylic acid to which sodium acetate hasbeen added. The whole is stirred until the diazo compound hasdisappeared and is thenv rendered alkaline and mixed with the diazocompound from 9.4 parts of 1-hydroxy-2-aminobenzene-4-sulfonic acid.After thisdiazo compound has also disappeared, the whole isfiltered andthe filtered dyestuff is suspended in 1000 parts of water. 20 parts ofcopper acetate are added and the suspension is heated for some time at80 C., after which the copper compound is separated by filtering. Theproduct dyes cotton yellow-brown shades.

A yellowish-brown dyestuff is likewise obtained by combining 42.9 parts.of the condensation product of the first paragraph of this example withthe diazo compound from 22.3 parts of 2-amino-4-ch10ro-1-hydroxybenzene- 6-sulfonic acid and converting thedyestuif thus obtained into its copper compound.

Further brown dyestuffs are obtained by combining 1 mol of the aforesaidternary condensation product indiiferent orders of succession with 1 molof a diazotized 1-aminobenzene-2-carbo-xylic acid, 1 mol of anortho-hydroxy-diazo compound, for examplel-hydroxy-2-amino-4-nitrobenzene or with 1 mol of a diazotizedaminoazo-dyestufi, for example with the diazotized azo-dyestuff from 1mol of diazotized l-aminonaphthalene-3:G-disulfonic acid and 1 mol ofmeta-toluidine.

Quite similar metalliferous dyestufis are also obtained if in thepreparation of the condensation product serving as coupling componentthe -18.4 parts of cyanuric chloride are replaced by 15 parts of 236-dichloro-4-methylpyrimidine, 19.9 parts of di-chloroquinazoline or21.4 parts or phenyldichlorotriazine. I

The formulae of the unmetallized dyestuffs may, for-example, be:

sisting of aromatic nuclei of the benzene and naphthalene series, itstands for a lake-forming groupin ortho-position to the -N=N-group, Pystands for the radical of a 5-pyrazo1one which is combined in l-positionwith the radical and in 4-position with the azo-group, y stands foraconnecting link of the group consisting of CH=CH- and CH2-CH2, and zfor a Cy-b-group, wherein 1) stands for a radical of an azo-dyestuff ofthe general formula R1--N=NR2 wherein the symbols R1 and R2 stand foraromatic nuclei selected from the group consisting of aromatic nuclei ofthe benzene and naphthaleneseries,;and Cy stands for a'connecting memberconsisting, of a. heterocyclic six membered nucleus which consists of atleast 3 and at the most 4 carbon atoms and of at least 2 and at the most3 nitrogen atoms, the nitrogen atoms being separated from one another byat least one carbon atom, one carbon atom adjacent to one nitrogen atombeing linked'by a group to the radical containing the pyrazolonenucleusand another carbon atom adjacent to one nitrogenatom being linkedby a group to one of the aromatic nuclei R1 and R2 of the radical b, theR1 nucleus being linked to the -N=NR2.group directly or through themedium of a .pyrazolone bridge which products form yellow to brownpowders, dissolve in water to yellow to orange-brown and olivesolutions, and dye cotton fast yellow to orange, brown 1 and olive WhatI claim is:

1. The metal compounds of the azo-dyestufis having in the free state thegeneral 'formula V s 01131 S o=H in which R stands for a nucleus of thegroup con- SOaH SOaH in which R stands for a-nucleus of the groupconsisting of aromatic nuclei of the benzene and naphthalene series, wstands for a lake-forming group in ortho-position to the -N=N-group, Pystands for the radical of a 5-pyrazolone which is combined in l-positionwith the radical OaH $0311 and in 4-position with the azo-group, 2stands for a Cy-b-group, wherein b stands for a radical of anazo-dyestuif of the general formula R1N=NRz wherein the symbols R1 andR2 stand for aromatic nuclei'selected from the group consistingofaromatic nuclei of the benzene and naphthalene series, and Cy stands fora connecting member consisting of a heterocyclic six membered nucleuswhich consists of at least 3 and at the most a carbon atoms and of atleast 2 and at the most 3 nitrogen atoms, the nitrogen atoms beingseparated from one another by at least one carbon atom, one carbon atomadjacent to one nitrogen atom being linked by a v N l1 group to theradical containing the pyrazolone nucleus and another carbon atomadjacent to one nitrogen atom being linked by a group to one ofthearomatic nuclei R1 and R2 of the radical b, the R1 nucleus beinglinked to the in Which R stands for a nucleus of the group consisting ofaromatic nuclei of the benzene and naphthalene series, :cstands for alake-forming group in ortho-position to the N=N-group, Py stands for theradical of a 5-pyrazolone which is combined in l-position with theradical C +Q SOsH soar:

and in l-position with the azo-group, 1 stands for a connecting link ofthe group consisting of CH=CI-I and CH2CH2, and z for a Cy-b-group,wherein b stands for a radical of an .azo-dyestuff of the generalformula R1N=NRz wherein the SYmbOISRJ. and R2 stand for aromatic groupto the radical containing the pyrazolone nucleus and another carbon atomadjacent to one nitrogen atom being linked by a in which R stands for anucleus of the group consisting of aromatic nuclei of the benzene andnaphthalene series, x stands for a lake-forming group inortho-position'in the -N=N-- group, Py stands for the radical of a5-pyrazolone which is combined in l-position with the radical S 03H S0311 and in 4-position with the azo-group, 2 stands for a Cy-b-group,wherein 1) stands for a radial of an azo-dyestuff of the general formulaR1N=N-R2 wherein the symbols R1 and R2 stand for aromatic nucleiselected from the group consisting of aromatic nuclei of the benzene andnaphthalene series, and Cy stands for a connecting member consisting ofa heterooyclic six membered nucleuswhich consists of at least 3 and atthe most .4 carbon atoms and of at least 2 and at the most 3 nitrogenatoms, the nitrogen atoms being separated from one another by at leastone carbon atom, one carbon atom adjacent to one nitrogen atom beinglinked by a r group to one of the aromatic nuclei R1 and R2 of theradical b, which products form yellow to brown powders, dissolve inwater to yellow to orange, brown and olive solutions, and dye cottonfast. yellow to orange, brown and olive tints which are particularlyfast to light. 7

5. The metal compounds of the azo-dyestuffs having in the free state thegeneral formula S OaH A 03H in which R stands for a nucleus of the groupconsisting of aromatic nuclei of the benzene and naphthelene series, :0stands for a lake-forming group in ortho-position to the N=N-group, Pystands for the radical of a b-pyrazolone which is combined in l-positionwith the radical and in 4-position with the azo-group, y stands for aconnecting link of the group consisting of -CH=CH-- and CH2-CH2--, and zfor a Cy-b-group, wherein b stands for a radical of an azo-dyestuff ofthe general formula R1-N=N-R2 wherein the symbols R1 and R2 stand foraromatic nuclei selected from the group consisting of aromatic nuclei ofthe benzene and naphthalene series, Cy stands for a connecting memberconsisting of a radical of the triazine nucleus, one carbon atom of thecyanuric nucleus being linked by a N I n H group to the radicalcontaining the pyrazolone nucleus and another carbon atom of thecyanurie nucleus being linked by a group to one of the aromatic nucleiBi and R2 of the radical b, which products form yellow to brown powders,dissolve in water to yellow to orange, brown and olive solutions, anddye cotton fast yellow to orange, brown and olive tints which areparticularly fast to light.

6. The metal compounds of the azo-dyestuffs having in the free state thegeneral formula Game-Q2 in which R stands for a nucleus of the groupconsisting of aromatic nuclei of the benzene and naphthalene series, a:stands for a lake-forming group in ortho-position to the N=N-group, Pystands for the radical of a 5-pyrazolone which is combined in l-positionwith the radical CH=OH 2 and in 4-position with the azo-group, 2 standsfor a Cy-b-group, wherein b stands for a radical of an azo-dyestuff ofthe general formula R1--N=NR2 wherein the symbols R1 and R2 stand foraromatic nuclei selected from the group consisting of aromatic nuclei ofthe benzene and naphthalene series, Cy stands for a connecting memberconsisting of a radical of the triazine nucleus, one carbon atom of thecyanuric nucleus being linked by a --CH=CH- and --CH2-CH2, and 2 for aCy-b-group, wherein 1) stands for a radical of an azo-dyestuff of thegeneral formula R1--N=NR2- wherein the symbols R1 and R2 stand foraromatic nuclei selected from the group consisting of aromatic nuclei ofthe benzene and naphthalene series, Cy stands for a connecting memberconsisting of a radical of the triazine nucleus, one

carbon atom of the cyanuric nucleus being linked by a i i l group to theradical containing the pyrazolone nucleus and another carbon atom of thecyanuric nucleus being linked by a group to one of thearomatic nuclei R1and R2 of the radical b, which products form yellow to brown powders,dissolve in water to yellow to orange, brown and olive solutions, anddye cotton fast yellow to orange, brown. and olive tints which areparticularly fast to light.

8. The copper compoundsof the azo-dyestuffs having in the free state thegeneral formula SOsH 80311 in which R stands for a nucleus of the groupconsisting of aromatic nuclei of the benzene and naphthalene series, 3:stands for a lake-forming group in ortho -position to the N=N-group, Pystands for the radical of a 5-pyrazolone which is combined in l-positionwith the radical and in l-position with the azo-group, 2 stands for aCy-b-group, wherein b stands for a radical of an azo-dyestuff of thegeneral formula R1N=N--R2 wherein the symbols R1 and R2 stand foraromatic nuclei selected from the group consisting of aromatic nuclei ofthe benzene and naphthalene series, Cy stands for a connecting memberconsisting of a radical of the triazine nucleus, one carbon atom of thecyanuric nucleus being linked by a group to the radical containing thepyrazolone nucleus and another carbon atom of the cyanuric nucleus beinglinked by a group to one of the aromatic nuclei of the radical b, whichproducts form yellow tobrown powders, dissolve in water to yellow toorange, brown and olive solutions, and dye cotton fast yellow to orange,brown and olive tints which are particularly fast .to light.

9. The copper compoundsof the azo-dyestuffs having in the free state thegeneral formula SO3H SOsH in which R stands for a nucleus of the groupconsisting of aromatic 'nuclei' of the benzene and naphthalene series, xstands for. a lake forming group in ortho-position to the N=N-group, Pystands for the radical of a 5-pyrazo1one which is combined inl-positionwith the radical SOaH' scan and in -position with the azo-group, ystands for a connecting link of the group consisting of -C H=CH- andCH2--CH2- and z for a its group, wherein one. 1; stands for an OH-groupand the other 1) for hydrogen, one t stands for a SOaI-I-group and theother tv fora;

group R and at having the signification given in claim 1, and the r b a'N=N -1|2 r group standing between the OI-I-group and the socH-group,which products form brown powders and dye cotton orange to brown tintsWhich are fast to light.

10. The copper compounds of the azo-dyestufi's having in the freestatethe general formula S 0311 g OsH in which It stands fora nucleus ofthe group consisting of aromatic nuclei of the benzene and naphthaleneseries, :0 stands fora lake-forming group in ortho-position to theN=N-group, by Py stands for the radical of a S-pyrazolone which iscombined in l-position with the radical QCH CHQZ I 803B 30.]: and in4-position with the azo-group, 2 stands for a and dye cotton orange tobrown tints which are fast to light. r

11. The copper compounds of the azo-dyestufis having in the free statethe general formula COOH u wherein Py stands for the radical'of a5-pyrazolone which is combined in 1position with the radical s0=H sea 1y standing for a connecting link of the group consisting of CII=CH and-CH2CH2-, and in 4-position with the azo-group, and wherein one 1)stands for an OH-group and the .other 1* for hydrogen, one i for aSOaH-group and the other if for a COOH group, the

group standing between the OH-group and the SO3H-group, which productsform brown powders and dye cotton orange to brown tints which are fastto light.

12. The copper compounds of the azo-dyestuffs having in the free statethe general formula wherein one 1) stands for an OH-group and the other11 for hydrogen, one If for a SOsH-group and the other t for a COOHgroup, the

group standing between the OI-I-group and the S 03H S 0:11

SOaH-group, which products form brown powders and dye cotton orange tobrown tints which are fast to light.

13. The copper compound of the azo-dyestuff having in the free state theformula (3H3 C=N COOH /N- CH=CH N= -o I II 50:11 80:11 H O which productdyes cotton brown tints fast to light.

14. The copper compound of the azo-dyestuff having in the free state theformula which yields on the vegetable fiber yellow tints fast to light.

15. The metal compounds of the dyestuffs having in the free state theformula 80:81 S OaH in which R1 and R2 stand for nuclei of the benzeneseries, :0 stands for a lake-forming group in ortho-position to the-N=N-group, 2 stands for a connecting member consisting of a triazinecompound, two carbon atoms of the cyanuric nucleus being each linkedto'agroup, Py stands for the radical of a 5-pyrazolone which is linked inl-position to the radical QQIMHQ SOsH SOaH and in 4-position to the azogroup, which products form yellow to brown powders, dissolve in water toyellow to orange and brown solutions and dye cotton similar tints fastto light.

16. The copper compounds of the dyestuffs having in the free state theformula I E H I in which R1 and R2 stand for nuclei of the henzeneseries, :1: stands, for a lake-forming group in ortho-position to theN=N-group, 2 stands for a connecting member consisting of a triazinecompound, two carbon atoms of the cyanuric OOOH nucleus being eachlinked to a ...]i]' BI group, Py stands for the radical of a5-pyrazo1one GOOH which is linked in l-position to the radical QGEEAHIQs 0311 s 03H and in 4-position to the azo group, which prod- SOsH uctsform yellow to brown powders, dissolve in water to yellow to orange andbrown solutions and dye cotton similar tints fast to light.

17. The copper compound of the azo-dyestufi having in the free state'bhe' formula; 1

CH=CH '8 OgH which yields on the vegetable fiber yellow tints 15 fast tolight.

